Hydroxycarboxylic Acids and Salts

ABSTRACT

Compositions which inhibit corrosion and alter the physical properties of concrete (admixtures) are prepared from salt mixtures of hydroxycarboxylic acids, carboxylic acids, and nitric acid. The salt mixtures are prepared by neutralizing acid product mixtures from the oxidation of polyols using nitric acid and oxygen as the oxidizing agents. Nitric acid is removed from the hydroxycarboxylic acids by evaporation and diffusion dialysis.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part application of co-pendingapplication Ser. No. 11/890,760, filed Aug. 6, 2007, which claims thebenefits of U.S. Provisional Patent Application No. 60/836,329, filedAug. 7, 2006, the disclosure of which is hereby incorporated byreference in its entirety including all figures, tables and drawings.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

The invention was made with Government support under Grant No.2003-364463-13003 and 2005-364463-15561 awarded by the USDA-CSRESS. TheGovernment has certain rights in the invention.

REFERENCE TO SEQUENCE LISTING, A TABLE, OR A COMPUTER PROGRAM LISTINGCOMPACT DISC APPENDIX

Not applicable

BACKGROUND OF THE INVENTION

This invention describes a method for synthesizing hydroxycarboxylicacid salts from polyols using nitric acid and oxygen as the oxidizingagents and applying the hydroxycarboxylic acid salts for uses thatinclude corrosion inhibiting materials and components of concrete.

Hydroxycarboxylic acids and hydroxycarboxylic acid salts are wellrecognized as corrosion inhibitors particularly effective in inhibitingmetal corrosion when the metal is in contact with water or an aqueoussolution (U.S. Pat. No. 2,529,177; U.S. Pat. No. 2,529,178; Erasmus,1971; Marukume, 1993; Hashimoto, 1976; and U.S. Pat. No. 4,120,655).

Nieland et al. taught that these hydroxycarboxylic acids, or saltsthereof, may contain a single carboxylic acid function, as in the caseof gluconic acid (U.S. Pat. No. 2,529,178), or multiple carboxylic acidfunctions as in the case of tartaric acid, a hydroxydicarboxylic acid,or citric acid, a hydroxytricarboxylic acid (U.S. Pat. No. 2,529,170).Nieland et al. have also taught that hydroxycarboxylic acids, or saltsthereof, with multiple carboxylic acid functions, such as tartaric acid(U.S. Pat. No. 2,529,170), generally exhibit better corrosion inhibitionproperties than do comparable hydroxymonocarboxylic acids, such asgluconic acid (U.S. Pat. No. 2,529,178).

Hydroxycarboxylic acids have also been shown to inhibit metal corrosionin aqueous salt brine such as sea water (Mor, 1971; Mor 1976; and Wrubl,1984) or formulated brine solutions (Kuczynski, 1979; Korzh, 1981;Sukhotin, 1982; and Abdallah, 1999), some employed for specificapplications, such as in industrial cooling systems (Sukhotin, 1982).

Metal corrosion inhibitors are commonly mixtures of components thatinclude hydroxycarboxylic acids, or salts thereof, the mixturessometimes described as providing a synergistic or cooperative effectwith components other than hydroxycarboxylic acids in corrosioninhibition rendering corrosion inhibition properties better than and/ordifferent from the individual components.

Crambes et al. describe (U.S. Pat. No. 4,120,655) the use ofhydroxycarboxylic acids selected from the group tartaric, citric andgluconic in addition to a phosphoric acid ester of an alkanolamine toinhibit the corrosion of ferrous metals in aqueous media includingaqueous media with high salt content. Numerous additional examples ofthe use of hydroxycarboxylic acids or hydroxycarboxylic salts inmixtures with components other than hydroxycarboxylic acids that serveas corrosion inhibiting agents have been reported (U.S. Pat. Nos.3,589,859; 3,711,246; 4,108,790; 5,891,225; 5,531,931; 5,330,683; andForoulis, 1971; Foroulis, 1972; Foroulis, 1973; Hiroshige, 1973; andBirk, 1976).

Sufrin et al. (U.S. Pat. No. 5,330,683) claims use of gluconate, withadditional components that include sorbitol or mannitol, as a corrosioninhibition agent in brine. However, it is clear from earlier reports(Mor, 1971; Mor 1976; Wrubl, 1984; and Kuczynsiki, 1979) that gluconatehad been reported effective as a corrosion inhibitor in brine.

Hydroxycarboxylic acids or salts thereof have a documented, long historyof use as corrosion inhibitors in liquid and solid media. They canfunction as corrosion inhibitors for metals in contact with water oraqueous solutions. They can serve as corrosion inhibitors in aqueoussolutions that have low to high salt concentrations, wherein those saltsinclude, but are not limited to alkali or alkaline metal salts ofhalides or other anionic components. They can function as corrosioninhibitors in the absence or presence of added substances. When theyfunction as corrosion inhibitors in the presence of added substances theadded substances may provide a positive synergistic corrosion inhibitoryeffect. Hydroxycarboxylic acids or salts forms with a single carboxylicacid function or multiple carboxylic acid functions can perform ascorrosion inhibitors. Salt forms of these hydroxycarboxylic acids ascorrosion inhibitors may have different cation components such as, butnot limited to, alkali and alkaline earth cations. Hydroxycarboxylicacids or salt forms can serve as corrosion inhibitors against a numberof metals, including, but not limited to iron, aluminum, copper andzinc. The hydroxycarboxylic acids or salt forms can serve as corrosioninhibitors in a multitude of applications where the use of nontoxicagents is an important advantage or requirement in the application,including but not limited to: cleaning of metal equipment; as corrosioninhibiting agents with corrosive salts, or other materials; for deicingpurposes on surfaces in cold weather; in applications involving storageor transport of water or aqueous solutions in metal containers orconduits; in concrete and concrete containing metal components such asstructural steel bars.

A need however remains for the availability of environmentally desirablematerials for use as corrosion inhibiting agents for a variety ofapplications. Furthermore, it is clear that there is a need for suchmaterials on a commercial scale for applications that include, but arenot limited to, corrosion inhibiting agent in use with deicing agentsfor use on roadways and pedestrian walkways affected by snow and iceduring cold weather periods, for use in concrete in contact with metalreinforcing bars, for cleaning boilers and other metal equipment.Materials that employ good corrosion inhibiting characteristics, areenvironmentally desirable, and can be produced economically on a largescale would be welcomed for commercial application on a large scale.

Hydroxycarboxylic acids and hydroxycarboxylic salts are also widelydescribed as admixtures to concrete used to favorably influencedifferent characteristics of concrete. Hydroxycarboxylic acids asadmixtures (additives) to concrete formulations can serve to favorablyeffect how the concrete is applied and provide favorable characteristicsof the concrete once it has hardened and is in use. Concrete admixturesinclude but are limited to roles as high-performance water reducers,improve concrete strength, and improve slump contraction (Wang, 2007).Such materials have been employed as set retarding additives (U.S.Published Patent Application No. US 2005-271431), as a set retarder fordownhole use (Drochon, 2003), as components to aid in production ofrapid setting cement (U.S. Published Patent Application No.2002-228008), as components of aqueous cementing fluids to increasecompression strength (U.S. Published Patent Application No.2;004-822459), as a setting controlling agent (e.g. tartaric acid, K Natartrate, and trisodium citrate) for use in production of cementhardened body (Sakamoto, 2004), as a component of a blowing material forrepairing degraded concrete (Araki, 2003), as a component of aplasticizer or superplasticizer in cement (Cerulli, 2002), as acomponent of a water-proof agent for concrete (Wu, 1999), as componentsof low-shrinkage cements useful for paving (Sekiguchi, 1993), ascomponents of lightweight cellular cement articles (Sakurada, 1989), asa component of a rust-preventing composition in cement for steelreinforcement (Nakano, 1986), as components of refractory cements foruse at high temperatures (Denki, 1985), as a component of rapidlyhardening cement (Denki II, 1985), as a component for retarding thesetting of cement mortars for large deep wells (Ene, 1982). Thepolyhydroxycarboxylic acids used as components of the setting retardantsdescribed in Ene were prepared by oxidation of molasses with nitric acidat 90° C. followed by neutralization.

Consequently, it is clear that there is a need for polyhydroxycarboxylicacids and their salts on a commercial scale for concrete productionapplications as illustrated herein and include but are not limited tothose uses, as they reflect only a portion of the reported uses inconjunction with concrete. Such materials are also environmentallydesirable in concrete and in related mortar applications, and theirlarge scale economic production would be welcomed for commercialapplication on a large scale.

Salts of glucaric acid are also sold as food supplements. Monopotassiumglucarate (potassium hydrogen glucarate) is used to maintain healthycholesterol levels already within normal ranges, whereas calciumD-glucarate is used to promote glucuronidation, a process in which thebody eliminates toxins and other adverse substances (U.S. Pat. Nos.4,845,123; 5,561,160; and 5,364,644). Monopotassium glucarate has arelatively low water solubility (about 10%) and calcium D-glucarate isvery insoluble in water. Therefore water soluble dipotassium D-glucaratehydrate (Styron, 2002) and monosodium monopotassium D-glucaratedihydrate (Styron, 2002) offer opportunities as food supplements andother applications where their water solubility is advantageous, andpreferred over the less water soluble glucarate salts.

Given the long documented history of the effectiveness ofhydroxycarboxylic acids as corrosion inhibitors and as components ofcement and products therefrom, and their attraction as materials forsafe use in the environment, it is desirable to have these materialsavailable in large quantities for numerous applications. It is alsodesirable to be able to employ a single, basic technology to theoxidation of these varied polyols for the production of the desiredhydroxycarboxylic acid salt products for use as corrosion inhibitingmaterials or concrete admixture materials. Furthermore, it is desirableto be able to apply the technology to a variety of polyol orcarbohydrate feedstocks to produce oxidation products with attractiveproperties that extend beyond those cited here. The currently employedcommercial methods of preparation of the common hydroxycarboxylic acidsor salts thereof are principally biologically induced transformations orfermentations, as for example in the production of tartaric acid (U.S.Pat. No. 2,314,831), gluconic acid (U.S. Pat. No. 5,017,485), and citricacid (U.S. Pat. No. 3,652,396). The fermentation of suitablecarbohydrate feedstocks for fermentation to the target acid requiresspecific microorganisms and special conditions to effect each of thefermentations, which are complex and multistep processes (WisconsinBiorefiners).

All patents, patent applications, provisional patent applications andpublications referred to or cited herein, are incorporated by referencein their entirety to the extent they are not inconsistent with theteachings of the specification.

BRIEF SUMMARY OF THE INVENTION

This invention describes novel chemical oxidation methods for polyols toprepare hydroxycarboxylic acids, as single oxidation products or inmixtures of oxidation products, applicable to commercial scaleproduction. The invention also describes conversion of the oxidationproducts to mixtures of salt products or to individual salt products.The oxidation products can be used as corrosion inhibiting materials fora variety of corrosion inhibiting applications, as concrete admixtures,and for other applications that can take advantage of the properties ofthe product mixtures or pure organic compounds isolated from themixtures. The preferred chemical oxidation method employs nitric acid asthe oxidizing agent in aqueous solution. The oxidation method isapplicable to polyols in general, of which carbohydrates providemultiple and diverse structurally different examples.

DETAILED DESCRIPTION OF THE INVENTION

This invention is directed to the chemical preparation ofhydroxycarboxylic acids, as single oxidation products or as mixtures ofoxidation products, applicable to commercial scale production, andemploying the oxidation products as corrosion inhibiting materials for avariety of corrosion inhibiting applications, as components of concrete,and for any other applications that can take advantage of theavailability of these oxidation products.

Hydroxycarboxylic acids can be considered as oxidation derivatives ofcarbohydrates or other polyols, a polyol meaning any organic compoundwith two or more alcohol hydroxyl groups. Such carbohydrates or polyolsinclude, but are not limited to: simple aldoses and ketoses such asglucose, xylose or fructose; simple polyols such as glycerol, sorbitolor mannitol; reducing disaccharides such as maltose, lactose, orcellobiose; reducing oligosaccharides such as maltotriose, maltotetrose,or maltotetralose; nonreducing carbohydrates such as sucrose, trehaloseand stachyose; mixtures of monosaccharides and oligosaccharides (thatmay include disaccharides); glucose syrups with different dextroseequivalent values; polysaccharides such as, but not limited to, starch,cellulose, arabinogalactans, xylans, mannans, fructans, hemicelluloses;mixtures of carbohydrates and other polyols that include one or more ofthe carbohydrates or polyols listed above.

The preferred chemical oxidation method employs nitric acid as theoxidizing agent in aqueous solution and has been described (U.S.Published Patent Application 2008/0033205). The nitric acid oxidationprocess described in Kiely and Hash (U.S. Published Patent Application2008/0033205) has two main components; an oxidation process, followed byseparation of nitric acid from organic products mixture, the organicprocucts mixture being primarily composed of hydroxycarboxylic acids.The final organic products mixture can be further treated to generate anorganic acids products mixture for use in acid forms or salt forms, orindividual isolated hydroxyacid products for use in acid or salt forms.

Applying the nitric acid oxidation method (U.S. Published PatentApplication 2008/0033205) to a glucose containing solution, produces amixture of oxidation products that includes gluconic acid, glucaricacid, tartaric acid, tartronic acid, 5-ketogluconic acid, and glycericacids, all of which are hydroxycarboxylic acids. It was anticipated thatsuch a mixture, water soluble and in salt form, would have someeffectiveness in iron corrosion inhibition tests. Employing standardiron corrosion inhibition testing as described here, it was determinedthat glucarate, from the hydroxydicarboxylic acid D-glucaric acid, was amore effective corrosion inhibiting agent than was gluconate, from thehydroxymonocarboxylic acid D-gluconic acid, as expected from the reportof Neiland et al. (U.S. Pat. Nos. 2,529,177; and 2,529,178) thathydroxydicarboxylic acids display greater corrosion inhibitingcharacteristics than hydroxymonocarboxylic acids. When the complexoxidation product mixture in salt form was evaluated for corrosioninhibition performance, it was found surprisingly that the mixture wasclose in corrosion inhibition effectiveness to that of glucarate alone,and more effective than gluconate alone (Table 1). However, what wasmore surprising was that when a portion of the high valued glucarate hadbeen removed from the oxidation mixture the effectiveness of theremaining product as a corrosion inhibitor was comparable to productmxture before the glucarate had been removed (Table 2). Since thedicarboxylic acid salt, such as a D-glucarate salt, is a more effectivecorrosion inhibitor than its corresponding monohydroxycarboxylic acidsalt, a D-gluconate salt, it was fully expected that the material fromwhich D-glucarate had been removed would be a less effective corrosioninhibitor than the material that still contained all of the glucarate.This finding adds economic value to the process since the high valueD-glucaric salts can be removed from the oxidation leaving behindmixtures with corrosion inhibiting properties that are comparable to themixtures with D-glucarate retained. The corrosion inhibitingeffectiveness testing results (Table 1) also demonstrate that oxidationmixtures from structurally variable polyols also show good properties ascorrosion inhibition agents. Thus, it has been determined that thechemical oxidation process gives rise to a complex product mixture, andthat mixture can be used effectively as a corrosion inhibitor, with allof the higher valued D-glucarate in the mixture, or with some of theD-glucarate removed. Furthermore, it is clear that the nitric acidoxidation of the polyols using nitric acid as the oxidizing agent andreaction solvent, can successfully generate mixtures of oxidized organicacids, which in salt form, can be used directly as effective corrosioninhibiting agents without any need for purification beyond removal ofthe nitric acid as described (U.S. Published Patent Application2008/0033205). The oxidative conversion of polyols to mixtures ofhydroxycarboxylic acids with nitric acid offers for the first time amethod for a rapid and effective large scale production method of theseacids in salt form as cost effective and environmentally desirablecorrosion inhibition agents and as beneficial cement components.

In addition to the oxidation product mixtures here described for use incorrosion inhibition applications, components of concrete and for otherpurposes, it is also desirable to use the oxidation process to preparesolid pure materials for particular or special applications thatinclude, but are not limited to, corrosion inhibition in deicingapplications such as when applied to surfaces for pedestrian orautomotive use. It is desirable that such materials have, in addition totheir corrosion inhibiting characteristics and environmentally favorableproperties, crystalline properties, as opposed to being solid powders.Furthermore, it is advantageous that such materials be readily watersoluble in order to perform well as corrosion inhibition materials inthe presence of water and water and ice/snow. Crystalline materials mixwell with solid deicers such as, but not limited to, sodium chloride ormagnesium chloride, and allow for normal spreading of the solid deicerand crystalline corrosion inhibitor without concern for the corrosioninhibiting agent being blown about and not applied properly. Two suchhighly crystalline forms of glucarate which can be produced from thenitric acid oxidation method of glucose containing starting materialsare dipotassium D-glucarate hydrate and monosodium monopotassiumD-glucarate dihydrate, respectively (Styron, 2002). These materials havecrystalline properties that make them very suitable for corrosioninhibition methods that employ solids, and in particular in combinationwith solid deicers. These materials are also readily soluble in water,making them very useful as corrosion inhibiting agents in aqueoussolution.

Salts of glucaric acid are also sold as food supplements. The two widelysold salts of D-glucaric acid are monopotassium D-glucarate (potassiumhydrogen D-glucarate) and calcium D-glucarate (U.S. Pat. Nos. 4,845,123;5,561,160; and 5,364,644), respectively, the former to maintain healthycholesterol levels already within normal ranges, and the latter topromote glucuronidation, a process in which the body eliminates toxinsand other adverse substances. Monopotassium D-glucarate has a relativelylow water solubility (about 10%), is a powdery substance, and solidcalcium D-glucarate is very insoluble in water. Therefore nicelycrystalline and water soluble dipotassium D-glucarate hydrate andmonosodium monopotassium D-glucarate dihydrate (Styron, 2002), availablefrom the oxidation process described here and potentially in largeamounts as co-products of the even larger commercial oxidation mixturesproducts markets employing the mixtures in non-food applications, suchas corrosion inhibiting agents and components of cement. Overall, theselatter salts offer opportunities and advantages in whatever applicationscan use them as cost effective, water soluble hydroxyacids, and in somespecific uses, e.g. food supplements, as water soluble D-glucaric acidsalts.

Producing the mixtures of oxidized polyols employing the chemicaloxidation process as described here has general advantages. Theseadvantages include that the process is a simple process, with highrecovery of products, that does not require a purification step to yieldthe product mixture useful for corrosion inhibition, concreteproduction, and other applications that can take advantage of theproperties of the mixtures, beyond the easy removal of the nitric acid.Additionally, the same basic process can be employed for all of thedesired oxidations employing suitable carbohydrates or other polyols.The same basic process is applicable to carbohydrates and other polyolsin general, and can be generally used for oxidations of thesefeedstocks. The oxidation product mixture, in its salt form, can be useddirectly for corrosion inhibiting applications without costly need forfurther purification. The oxidation product mixture, in its salt formand/or acid form, can be used directly as a component of concretewithout costly need for further purification. The oxidation productmixture, after removal of a higher valued pure product (or products),can be used for corrosion inhibiting applications. The oxidation productmixture, after removal of a higher valued pure product (or products),can be used for corrosion inhibiting applications. The oxidation productmixture, after removal of a higher valued pure product (or products),can be also be used as a component of concrete. A pure product isolatedfrom the oxidation mixture can be used for corrosion inhibitingapplications or different applications including as a food supplement. Anumber of renewable polyol or carbohydrate feedstocks can be employed asoxidation substrates to produce hydroxycarboxylic acid products withcorrosion inhibiting characteristics. A number of renewable polyol orcarbohydrate feedstocks can be employed as oxidation substrates toproduce hydroxycarboxylic acid products for use as components ofconcrete. The oxidation products formed in these processes can be usedfor any number of applications requiring materials with environmentallydesirable properties coupled with corrosion inhibiting properties. Theoxidation products formed in these processes can be used for any numberof applications requiring materials with environmentally desirableproperties coupled with desirable properties as components of concretepreparations. The corrosion inhibiting applications include, but are notlimited to: use in water systems with little to no additional dissolvedsubstances; use in environments in contact with sea water for corrosioninhibiting applications; use in brine or water cooling applications; usein boiler and other metal equipment surface cleaning applications; useas corrosion inhibiting applications in brine solutions applied fordeicing; use in oil well muds as corrosion inhibiting materials; use incement and concrete as corrosion inhibiting materials. The availabilityof different mixtures as corrosion inhibiting agents or components ofconcrete opens up commercial potential for such mixtures as costeffective, environmentally favorable materials that can be readily andefficiently produced from renewable polyols and carbohydrates.

The following examples are offered to further illustrate but not limitboth the compositions and the methods of the present invention. Allpercentages are by weight and all solvent mixture proportions are byvolume unless otherwise noted.

EXAMPLE 1 Corrosion Test Methods

Salt products prepared by the nitric acid oxidation methods and work upprocedures described in this invention were evaluated for theircorrosion inhibiting properties according to standard testing methods.Corrosion tests were performed according to the National Association ofCorrosion Engineers (NACE) Standard TM0169-95 modified by the PacificNorthwest Snowfighters (PNS) (NACE TM0169-95).

The test procedure was modified to use 30 mL of a 3% solution ofinhibitor per square inch of total coupon surface area. Stamped andnumbered steel TSI coupons which met the ASTM F436 Type 1 requirementwith a Rockwell hardness of C 38-45 were used for each corrosion test.Approximate coupon dimensions are 1.37 in. outer diameter,0.60 in. innerdiameter, and 0.10 in. thickness with a density of 7.85 grams per cubiccentimeter. Coupons were placed in a sealed container on a rock tumblerwith a non-abrasive cleanser for 30 minutes to remove surface grease andimpurities. Coupons were wiped with acetone to remove any additionalgrease, rinsed with deionized water, and then acid etched with an 18.5%HCl solution for approximately 3 minutes. The coupons were rinsed withtap water, rinsed with deionized water, patted dry and placed inchloroform for 15 minutes. The coupons were removed from chloroform andallowed to air dry in a ventilated hood for 1 hour. Each coupon was thenweighed to the nearest 0.1 mg. at least two times to ensure a consistentweight.

Distilled water was used to prepare each solution and control standard.Sodium chloride was used as the salt standard. A 3% solution of NaCl(EMD, analyzed reagent grade, 9.6 g) in distilled water (310.4 g) wasprepared as a salt standard(w/v). Each test solution was prepared with3% NaCl, 310.4 g distilled water, and a corrosion inhibitor. Two NaClsalt solutions containing each inhibitor were prepared at 3% and 1.5%inhibitor concentration (by weight of salt, 288 mg and 144 mg,respectively). Approximately 300 mL of each solution in distilled waterwas transferred to a clean 500 mL Erlenmeyer flask equipped with arubber stopper which had been drilled to allow a thin line attached to aplastic rod to run through it. The pH of each solution was measured andrecorded. Aqueous 5% sodium hydroxide was carefully added (1-2 drops)until a basic pH was established for each test solution. The pH of theNaCl and H₂O control solutions was not altered. Three coupons wereattached to a plastic bar suspended within each flask through thestopper hole. A timed device raised and lowered the test coupons so theywere immersed in the test solution for 10 minutes of each hour for a 72hour period. Tests were conducted at room temperature.

After the 72 h. test period, the coupons were quickly removed fromsolution, rinsed under tap water and vigorously rubbed to remove anysurface corrosion material. The coupons were then placed in shallowevaporating dishes containing a cleaning solution of concentratedhydrochloric acid, stannous chloride (50 g/liter), and antimony chloride(20 g/liter) for 15 minutes. The coupons were removed from the acidsolution, rinsed vigorously under tap water, and returned to thecleaning solution for an additional 15 minutes. The coupons were againremoved from the acid solution, rinsed under tap water, rinsed underdeionized water, patted dry, and placed in a vessel containingchloroform for 10 minutes. The coupons were removed from the chloroformand allowed to air dry under a ventilated hood for 1 hour before beingweighed to the nearest 0.1 mg. Each coupon was weighed twice to ensure atrue final weight. Corrosion rate in mils per year (MPY) was calculatedfrom the measured weight loss of each coupon using the followingequation:

${MPY} = \frac{{weight}\mspace{14mu} {loss}\mspace{11mu} {({mg}) \cdot 534}}{{area}\mspace{11mu} {\left( {cm}^{2} \right) \cdot {time}}\mspace{11mu} {(h) \cdot {metal}}\mspace{14mu} {density}}$metal  density = 7.85  g/cc time = 72  hours

The corrosion value for the control solution of distilled H₂O was alsocalculated. The MPY value of the distilled water was subtracted from theMPY value of each sample solution containing 3% NaCl to provide acorrected MPY value, which is noted as MPY′. The MPY′ values of each ofthree coupons in the test solution were averaged to determine the MPY′value of the entire test solution. A Percent Effectiveness value, whichmeasures the rate of corrosion of sample as compared to the corrosionvalue for salt, was determined. The Percent Effectiveness of eachsolution is calculated as follows:

${{Percent}\mspace{14mu} {Effectiveness}} = {\frac{\left( {{{MPY}\mspace{14mu} {of}\mspace{14mu} {inhibitor}\mspace{14mu} {sample}} - {{MPY}\mspace{14mu} {of}\mspace{14mu} H_{2}O}} \right)}{\left( {{{MPY}\mspace{14mu} {of}\mspace{14mu} {NaCl}} - {{MPY}\mspace{14mu} {of}\mspace{14mu} H_{2}O}} \right)} \cdot 100}$or${{Percent}\mspace{14mu} {Effectiveness}} = {\frac{{MPY}^{1}\mspace{14mu} {of}\mspace{14mu} {inhibitor}\mspace{14mu} {sample}}{{MPY}^{1}\mspace{14mu} {of}\mspace{14mu} {NaCl}} \cdot 100}$

Accordingly, the distilled H₂O control has a Percent Effectiveness valueof 0%, while the 3% NaCl control has a 100% Percent Effectiveness value.The corrosion inhibitor samples have Percent Effectiveness valuesbetween 0% and 100%. In order for a material to be acceptable as acorrosion inhibitor, the Percent Effectiveness of the material must havea value of 30% or less as defined by PNS.

Table 1 shows corrosion rates (MPY), corrected corrosion rates (MPY′),and percent effectiveness of water, 3% NaCl solution, and 3% NaClsolutions containing corrosion inhibitors derived from salts ofhydroxycarboxylic acids. Each sample was dissolved in distilled waterand the sample solution was made basic (>pH 8) with the exception ofsodium D-gluconate and commercial liquid sodium gluconate product testedat their natural pH values of 6.1 and 3.2, respectively.

TABLE 1 Corrosion Rates (MPY), Corrected Corrosion Rates (MPY¹), andPercent Effectiveness of Corrosion Inhibitors in 3% NaCl Solutions*Inhibitor Percent Corrosion Inhibitor Concentration (%)* MPY MPY¹Effectiveness None (H₂O control) 0 5.650 0.000 0.00% sodium D-gluconate1.5 24.596 20.313 36.98% sodium D-gluconate 3.0 22.786 18.503 33.45%commercial liquid gluconate product 3.0 34.580 28.928 67.63% sodiumpotassium D-glucarate 1.5 23.726 19.443 35.28% sodium potassiumD-glucarate 3.0 20.939 16.656 29.84% nitric acid oxidized 95-99% liquid1.5 24.871 20.588 37.52% dextrose nitric acid oxidized 95-99% liquid 3.021.424 15.774 30.78% dextrose nitric acid oxidized 41-44% liquid 1.534.666 29.016 56.63% dextrose nitric acid oxidized 41-44% liquid 3.029.904 24.254 47.34% dextrose nitric acid oxidized sucrose 3.0 21.64215.992 31.21% None (NaCl control) 0 57.574 51.235 100.00%*Concentrations are given in weight %.Table 2 shows corrosion rates (MPY), corrected corrosion rates (MPY′),and percent effectiveness of water, 3% NaCl solution, and 3% NaClsolutions containing corrosion inhibitors derived from nitric acidoxidized 95-99% liquid dextrose and nitric acid oxidized 95-99% liquiddextrose from which some D-glucarate has been removed. Each sample wasdissolved in distilled water and the sample solution was made basic (>pH8).

TABLE 2 Corrosion Rates (MPY), Corrected Corrosion Rates (MPY¹), andPercent Effectiveness of Nitric Acid Oxidized 95-99% Liquid Dextrose andNitric Acid Oxidized 95-99% Liquid Dextrose with Less D-Glucarate asCorrosion Inhibitors in 3% NaCl Solutions* Inhibitor Percent CorrosionInhibitor Concentration (%)* MPY MPY¹ Effectiveness H₂O (control) 0.005.027 0.000 0.00% nitric acid oxidized 95-99% 3.25 19.464 14.434 24.03%liquid dextrose nitric acid oxidized 95-99% 3.25 15.833 10.807 17.99%liquid dextrose less D- glucarate nitric acid oxidized 95-99% 3.9017.149 12.122 20.18% liquid dextrose nitric acid oxidized 95-99% 3.9014.568 9.542 15.88% liquid dextrose less D- glucarate nitric acidoxidized 95-99% 4.55 16.041 11.013 18.33% liquid dextrose nitric acidoxidized 95-99% 4.55 15.516 10.489 17.46% liquid dextrose less D-glucarate NaCl (control) 0.00 67.238 62.211 100.0% *Concentrations aregiven in weight %.

It is clear from the results provided in Tables 1 that by increasing theconcentration of corrosion inhibitor in 3.0% sodium chloride solutionthere is a marked improvement (lowering) of the percent effectiveness(PNS score). It is also clear that the nitric acid oxidation productfrom the oxidized 95-99% liquid dextrose product performs close to thatof a pure form of glucarate and better than gluconate, with the formertwo materials at about the preferred 30% effectiveness value andgluconate at a higher value. The commercial liquid gluconate productshowed a very high (poor performance) corrosion effectiveness score ofgreater than 60%. The glucarate and oxidized dextrose materials wereadjusted to a higher pH than gluconate and commercial liquid gluconatebecause the former materials have significantly higher water solubility(ca. 70%) than the gluconate product (ca. 60%) at the higher pH, and canbe transported and used at the higher pH value and the correspondinglyhigher concentration than can gluconate.

It has been demonstrated here, and in earlier reports, that adihydroxyacid such as D-glucaric acid is a better corrosion inhibitingagent than the corresponding monohydroxyacid, e.g., D-gluconic acid.Consequently, it was anticipated that when the nitric acid oxidized95-99% liquid dextrose product used in the corrosion rate tests had someof the glucarate removed from this oxidation mixture, the resultingmaterial would be a less effective corrosion inhibiting material thanthe material that still contained all of the glucarate. Surprisingly,contrary to this obvious expectation, the nitric acid oxidized 95-99%liquid dextrose less glucarate samples were comparable as corrosioninhibiting materials to those from nitric acid oxidized 95-99% liquiddextrose with no glucarate removed (Table 2). This unexpected resultfurther raises the value of the overall oxidation process describedhere, because some high value D-glucaric acid can first be removed fromthe oxidation product mixture, leaving a product mixture that has goodcorrosion inhibiting properties.

Consequently, the oxidized products described in this invention offerseveral advantages over single hydroxyacids as corrosion inhibitors thatinclude, but are not limited to: 1) they have very high watersolubilities which allows for lowered cost of transport and use; 2) theyhave significantly enhanced performance at pH values above 7 whichdecreases the amount of material that is used in a corrosion inhibitingapplication and lowers the cost of that use; 3) they do not requirepurification to single materials to effectively inhibit corrosion, animportant production cost lowering factor in their production, 4) somehigh value D-glucaric acid can be easily separated from the oxidationmixture of glucose based substrates, leaving a product behind thatoffers corrosion inhibiting properties that are comparable to themixture that contained all of the glucaric acid.

EXAMPLE 2 Samples Prepared as Concrete Admixtures

The samples prepared as concrete admixtures were of the type listed inTable 2 Sample I being oxidation mixtures as described with no glucarateremoved, Sample II being oxidation mixtures as described with someglucarate removed, and Sample III being a single admixture substancefrom the oxidation, i.e., monopotassium D-glucarate.

-   -   I nitric acid oxidized 95-99% liquid dextrose    -   II nitric acid oxidized 95-99% liquid less D-glucarate    -   III monopotassium D-glucarate

A pH greater than 9 was established for Samples I-II by addition ofsodium hydroxide, whereas the pH of the Sample III solution wasestablished as greater than 9 by addition of potassium hydroxide.

A.—Admixture Sample Preparation

Numerous samples were prepared from the dextrose oxidation product to betested as potential concrete admixtures. Each sample was varied bycontrol of reaction conditions, work-up procedure and product analysisby ion chromatography for D-glucarate, D-gluconate, nitrate andadditional organic acids in the final product. Whole product samples(I), whole product with some D-glucarate removed (II), and singleproduct glucarate (III) were prepared and submitted for admixtureanalysis. All samples were tested and analyzed by TEC Services: Testing,Engineering and Consulting Services, Inc., 235 Buford Dr.,Lawrenceville, Ga. 30045.

B.—Concrete Admixture Test Methods

Salt products prepared by the nitric acid oxidation methods and work upprocedures described in this invention were evaluated for their concreteadmixture properties according to standard testing methods. Admixturetests were performed according to ASTM Standard C494/C494 M-05a, 2005“Standard Specifications for Chemical Admixtures for Concrete”, ASTMInternational, West Conshohocken, Pa., 2005.

C.—Analysis of Admixtures

Standard concrete mixtures of cement, water, rock, sand, and airentraining agent were prepared for laboratory testing of concreteadmixtures. Approximately 4 L of each sample were prepared at 20%concentration of solids after being made basic with sodium hydroxide andsubmitted for admixture analysis. The mono potassium D-glucarate productwas prepared at 10% solids after being made basic with potassiumhydroxide. Each sample was added to a standard concrete mixture andtested for performance and efficiency as a concrete admixture as definedby the ASTM Standard C494/C494 M-05a. The following physicalrequirements were measured for each admixture: water content, slump,percent air, weight, time of initial and final set, and compressivestrength. A concrete sample without the addition of an admixture wasestablished as a control sample. Each admixture sample was added toseparate concrete test mixtures and measured against the control. Onecontrol mixture and one trial mixture containing each of the admixtureswas prepared and tested for fresh and hardened concrete properties.Samples were classified as admixture types as defined by ASTM C494standards. There are eight types of admixtures: Type A (water reducing),Type B (set retarding), Type C (accelerating), Type D (waterreducing/set retarding), Type E (water reducing/accelerating), Type F(high range water reducing), Type G (high range water reducing/setretarding), and Type H (mid-range water reducing). Admixture sampleswere added to the concrete test mixtures in optimal doses to meet thephysical requirements of Type A and Type D admixtures. Samples I-IIIwere also tested as potential Type A admixtures.

Type A admixtures maximize the benefits of increased hydration inhardened and plastic concrete (Collepardi, 1995). The specifications forType A water reducing admixtures, as well as the testing results fromSamples I-III are presented in Table 3. As defined in Section 3 of ASTMC494/C494-05a, Type A admixtures must reduce the quantity of mixingwater required to produce concrete of given consistency by 5-12% andstay within a defined time of set comparable to the control, unlike TypeD water reducers/set retarders. Sample I-III were all dosed atapproximately 2.5 oz/cwt cement; however, due the higher concentrationsof Samples I and II, the effective dose (solid admixture amount) wasalmost twice the amount of Sample III. While all Samples meet waterreduction, time of set, and compressive strength standards for Type Awater reducters, the higher effective doses of Samples I and II appearto give better performance as evidenced by the higher percent of waterreduction.

Type D admixtures encompass the properties of both a set retarder and awater reducer. To meet specifications, Type D admixtures must increasethe time of set up to 3.5 h and reduce the amount of requisite mixingwater up to 12%. As specified in Table 4, Type D admixtures must meetthe compressive strength requirements of at least 110% of the concretecontrol. The specifications for Type D (water reducing/set retarding)admixtures, as well as the testing results from Samples I-III arepresented in Table 4. Dosage amounts of any admixture are relative tothe amount of cement in the entire concrete mixture. For example, SampleI was dosed at 2.9 oz/cwt cement in order to meet the ASTM requirementsfor a Type D admixture as opposed to the 2.4 oz/cwt required to meetType A specifications (Table 3). This minor increase in dosage issignificant in defining and applying Sample I as either a Type D or aType A admixture. In addition to increasing the set times, waterreduction was also increased at a higher dose of Sample I. Samples IIand III also met Type D admixture standards at higher doses of 4.0-5.0oz/cwt cement. Samples I-III meet compressive strength and durabilitystandards over time. As Type D admixtures, Samples I-III improve thehardened properties of concrete and ensure even set. Type D admixturesare essential in warmer climates, ensuring lengthened time of set andimproved workability while conserving water. Table 4 demonstrates theeffectiveness of Samples I-III as Type D admixtures. Clearly, changingthe dosage of admixtures of Samples I-III, and other samples ofhydroxycarboxylic acids produced using the oxidation process describedhere employing a range of process conditions and from different polyols,underscores the versatility of such oxidation products as useful fordifferent admixture types.

In summary, the testing results presented in Tables 3 and 4 illustratethe versatility and effectiveness of products from oxidation of a polyolwith nitric acid as concrete admixtures. As illustration, Samples I andII are applied at lower concentrations of solids than most admixturescurrently on the market (Collepardi, 1995).

TABLE 3 Mix Proportions and Test Results for Dextrose Oxidation Productsas Type A (water reducing) Admixtures Type A Admixture Control I II IIISpecifications (Concentration) (0%) (20%) (20%) (10%) (ASTM C494) Cement(lbs/cu yd) 517 517 517 517 512-521 Water (lbs/cu yd) 287.5 270 265 273≦95% of control Air Entrainment 0.58 0.41 0.39 0.40 (oz/cwt) AdmixtureDose 0.0 2.4 2.4 2.5 (oz/cwt) Solid Admixture Amt 0.0 0.48 0.48 0.25(oz) Glucarate 0.0 40 35 100 Concentration (% of solid) NitrateConcentration 0.0 6 4 0.0 (% of solid) Water reduction (% 0.0 6.00 7.585.04 ≧5.0% of control) Slump (in.) 3.50 3.00 3.00 3.00 3″-4″ Air (%)5.50 5.50 5.00 5.50 5-7 (±0.5 of control) Initial Set Time 0.00 1:13later 1:02 later 0:47 later 1:00 earlier-1:30 Difference later Final SetTime 0.00 1:28 later 1:09 later 0:57 later 1:00 earlier-1:30 Differencelater Compressive Strength psi (% of control) 7 days 3150 3650 NA 3930 110% (116%) (125%)

TABLE 4 Mix Proportions and Test Results for Dextrose Oxidation Productsas Type D (water reducing/set retarding) Admixtures Type D AdmixtureControl I II III Specifications (Concentration) (0%) (20%) (20%) (10%)(ASTM C494) Cement (lbs/cu yd) 517 517 517 517 512-521 Water (lbs/cu yd)287.5 264 273 273 ≦95% of control Air Entrainment (oz/cwt) 0.58 0.390.32 0.34 Admixture Dose (oz/cwt) 0 2.9 5.0 4.8 Solid Admixture Amt (oz)0 0.58 1 0.48 Glucarate Concentration 0 40%  28% 100% (% of solid)Nitrate Concentration 0  6%  5%  0% (% of solid) Water reduction 0.08.10 5.04 5.04 ≧5.0% (% of control) Slump (in.) 3.5 3.0 3.5 3.5 3″-4″Initial Set Time 0.00 1:30 later 2:36 later 1:27 later 1:00-3:30 laterDifference Final Set Time Difference 0.00 1:46 later 2:43 later 2:06later 1:00-3:30 later Compressive Strength, psi (% of control)  7 days3150 NA 3980 3690  110% (126%) (117%) 28 days 4290 5530 5080  110%(129%) (118%)

EXAMPLE 3 General Methods

Solutions were concentrated in vacuo (15-25 mbar) using a rotaryevaporator and water bath at 50° C. pH measurements were made with aThermo Orion 310 pH meter (Thermo Fisher Scientific, Inc., Waltham,Mass., USA) which was calibrated prior to use. Oxidations were carriedout in Mettler Toledo LabMax reactor, designed to operate as a computercontrolled closed-system reactor. The Labmax was fitted with atop-loading balance, a liquid feed pump, an oxygen Sierra flow valve, amechanically driven stirring rod, a thermometer, a 2 liter thermaljacketed flask, an FTS recirculating chiller, a pressure manifold fittedwith pressure relief valves and pressure gauge, and a personal computerwith CamileTG v1.2 software. The software installed allows the operatorto program experiments based on specific parameters and conditions.Oxidation procedures are readily changed as needed as illustrated inExamples 9-13.

Examples of, but not limited to, preparation of polyol aqueous solutionssuitable for nitric acid oxidation.

EXAMPLE 4 D-Glucose Solution Preparation

Aqueous 62.3% D-glucose solution used in the oxidations was prepared byadding solid D-glucose (325.0 g, 1.50 mol) to 195.0 grams of deionizedwater in a screw-capped flask containing a stir bar. Prior to addingsolid D-glucose to the water, the water was heated to ca. 60° C. withstirring. Once the D-glucose was dissolved, the solution was allowed tocool to ambient temperature and dry sodium nitrite (1.20 g) was added.The total weight of the solution was 521.5 g.

EXAMPLE 5 Liquid Dextrose Solution (95-99% Dextrose Equivalent)Preparation

Aqueous 62.3% liquid dextrose (95-99% dextrose equivalent) solution usedin the oxidation was prepared by adding semi-solid liquid dextrose,StaleyDex® 95 Liquid Dextrose (457.8 g, dry substance 71.0%) to 62.25grams of deionized water in a screw-capped flask containing a stir bar.The flask and its contents were heated to ca. 60° C. to dissolve thesemi-solid liquid dextrose. Once the liquid dextrose was dissolved, thesolution was allowed to cool to ambient temperature and dry sodiumnitrite (1.20 g) was added. The total weight of the solution was 521.5G.

EXAMPLE 6 Lower Dextrose Equivalent (41-45%) Corn Syrup SolutionPreparation

Aqueous 62.3% liquid corn syrup used in the oxidation was prepared byadding viscous corn syrup 41-45% dextrose equivalent, Staley®1300 CornSyrup (404.9 g, dry substance 80.3%) to 115.2 grams of deionized waterin a screw-capped flask containing a stir bar. The flask and itscontents were heated to ca. 60° C. to dissolve the viscous corn syrup.Once dissolved, the solution was allowed to cool to ambient temperatureand dry sodium nitrite (1.20 g) was added. The total weight of thesolution was 521.3 g.

EXAMPLE 7 Preparation of a Nitric Acid Hydrolyzed Starch Mixture forDirect Nitric Acid Oxidation

Aqueous 50% hydrolyzed starch mixture was prepared by adding corn starch(50.0 g) in portions (5.0 g) over a 2.25 h period to 35% nitric acid(50.0 g) at 65° C. . The mixture was suitable for direct nitric acidoxidation as described in Examples 9-13.

EXAMPLE 8 Sucrose Solution Preparation

The aqueous 62.3% sucrose solution used in the oxidations was preparedby adding solid sucrose (308.0 g, 0.75 mol) to 184.9 grams of deionizedwater in a screw-capped flask containing a stir bar. Prior to addingsolid sucrose to the water, the water was heated to ca. 60° C. withstirring. Once the sucrose was dissolved, the solution was allowed tocool to ambient temperature and dry sodium nitrite (1.20 g) was added.The total weight of the solution was 494.0 g.

Examples of, but not limited to, nitric acid oxidation of polyolprocedures

EXAMPLE 9 Oxidation Procedure: 1:4 Polyol to Nitric Acid Molar Ratio

The Recipe Menu was accessed using the Labmax Camille TG v1.2 software.Stage 1—the temperature was set at 25° C.; the stirring rod speed set at200 rpm (and held constant throughout all remaining stages); time setfor 1 minute duration. Stage 2—the temperature was set at 25° C., andthe pressure set at 0.25 bar, time set for 3 minutes. Stage 3—thetemperature was set at 25° C., and the pressure set at 0.25 bar aboveatmosphere, and 43.3 grams of a 62.3% (w/w) D-glucose solution,containing 0.23% by weight of sodium nitrite, set to be added over 30minutes. Stage 4—the temperature was set at 25° C., and the pressuremaintained at 0.25 bar, and the duration was set at 10 minutes. Stage5—the temperature was set at 25° C., and the pressure maintained at 0.25bar, and 172.9 grams of a 62.3% (w/w) D-glucose solution, containing0.23% by weight of sodium nitrite was set to be added over 90 minutes.Stage 6—the temperature was set at 25° C., and pressure maintained at0.25 bar, time set for 5 minutes. Stage 7—the temperature was increasedto 30° C., and the pressure was increased to 0.50 bar, and the time setto 60 minutes duration. Stage 8—the temperature was set at 30° C., andthe pressure maintained at 0.50 bar, and time was set for over 90minutes. Stage 9—the reactor temperature was set to cool to 25° C. over10 minutes. Once the reaction was programmed to proceed as indicated,nitric acid (68-70%, 187 mL, ca. 3.0 mol) was added to the reactor. Thereaction recipe was initiated and starting at stage 1, the reactor wasclosed to the atmosphere. When the reaction had progressed through allof the stages, the reaction mixture was removed from the reactor throughthe bottom valve of the reactor.

EXAMPLE 10 Oxidation Procedure: 1:3 Polyol (D-Glucose) to Nitric AcidMolar Ratio

The Recipe Menu was accessed using the Labmax Camille TG v1.2 software.Stage 1—the temperature was set for 25° C. (and held constant throughoutall remaining stages) and the stirring rod speed set at 200 rpm (andheld constant throughout all remaining stages); 282 mL (68-70%, 4.5 mol)nitric acid was added to the reactor through a top port; time was setfor 1 minute duration. Stage 2—the pressure was set at 0.25 bar aboveatmosphere, time set for 3 minutes duration (and held constantthroughout all remaining stages). Stage 3—added to the nitric acid was86.6 grams of a 62.3% (w/w) D-glucose solution containing 0.23% byweight of sodium nitrite, set to be added over 30 minutes. Stage4—temperature and pressure held constant for a duration of 10 minutes.Stage 5—added to the nitric acid was 345.8 grams of a 62.3% (w/w)D-glucose solution containing 0.23% by weight of sodium nitrite, set fora duration of 90 minutes. Stage 6—temperature and pressure held constantfor a duration of 20 minutes. Once the reaction was programmed toproceed as indicated the reaction recipe was initiated and starting atstage 1, the reactor was closed to the atmosphere. When the reaction hadprogressed through all of the stages, the reaction mixture was removedfrom the reactor through the bottom valve of the reactor.

EXAMPLE 11 Oxidation Procedure 1:3 Polyol (95-99% Dextrose Equivalent,Liquid Dextrose Solution) to Nitric Acid Molar Ratio

The Recipe Menu was accessed using the Labmax Camille TG v1.2 software.Stage 1—the temperature was set for 25° C. (and held constant throughoutall remaining stages) and the stirring rod speed was set at 200 rpm (andheld constant throughout all remaining stages); 282 mL (68-70%, 4.5 mol)nitric acid was added to the reactor through a top port; time was setfor 1 minute duration. Stage 2—the pressure was set at 0.25 bar aboveatmosphere, time set for 3 minutes duration (and held constantthroughout all remaining stages). Stage 3—added to the nitric acid was86.6 grams of a 62.3% (w/w) liquid dextrose solution, StaleyDex®95solution, containing 0.23% by weight of sodium nitrite, set to be addedover 30 minutes. Stage 4—temperature and pressure held constant for aduration of 10 minutes. Stage 5—added to the nitric acid was 345.8 gramsof a 62.3% (w/w) liquid dextrose solution, StaleyDex®95, containing0.23% by weight of sodium nitrite, set for a duration of 90 minutes.Stage 6—temperature and pressure held constant for a duration of 20minutes. Once the reaction was programmed to proceed as indicated thereaction recipe was initiated and starting at stage 1, the reactor wasclosed to the atmosphere. When the reaction had progressed through allof the stages, the reaction mixture was removed from the reactor throughthe bottom valve of the reactor.

EXAMPLE 12 Oxidation Procedure 1:3 Polyol (41-45 % Dextrose EquivalentCorn Syrup Solution) to Nitric Acid Molar Ratio

The Recipe Menu was accessed using the Labmax Camille TG v1.2 software.Stage 1—the temperature was set for 30° C. (and held constant throughoutall remaining stages) and the stirring rod speed was set at 200 rpm (andheld constant throughout all remaining stages); 282 ml (68-70%, 4.5 mol)nitric acid was added to the reactor through a top port; time was setfor 1 minute duration. Stage 2—the pressure was set at 0.25 bar aboveatmosphere, time set for 3 minutes duration (and held constantthroughout all remaining stages). Stage 3—added to the nitric acid was86.6 grams of a 62.3% (w/w) solution of 41-45% dextrose equivalent cornsyrup, Staley®1300, solution containing 0.23% by weight of sodiumnitrite, set to be added over 30 minutes. Stage 4—temperature andpressure held constant for a duration of 10 minutes. Stage 5—added tothe nitric acid was 345.8 grams of a 62.3% (w/w) ) solution of 41-45%dextrose equivalent corn syrup, Staley®1300, solution containing 0.23%by weight of sodium nitrite, set for a duration of 90 minutes. Stage6—temperature and pressure held constant for a duration of 20 minutes.Once the reaction was programmed to proceed as indicated the reactionrecipe was initiated and starting at stage 1, the reactor was closed tothe atmosphere. When the reaction had progressed through all of thestages, the reaction mixture was removed from the reactor through thebottom valve of the reactor.

EXAMPLE 13 Oxidation Procedure 1:6 Polyol (Sucrose) to Nitric Acid MolarRatio

The Recipe Menu was accessed using the Labmax Camille TG v1.2 software.Stage 1—the temperature was set for 35° C. and the stirring rod speedwas 200 rpm (and held constant throughout all remaining stages); 312.5ml (68-70%, 5.0 mol) nitric acid was added to the reactor through a topport; time was set for 1 minute duration. Stage 2—temperature was set at35° C., the pressure was set at 0.25 bar above atmosphere(and heldconstant throughout all remaining stages), time set for 3 minutesduration. Stage 3—temperature was set at 35° C., added to the nitricacid was 82.2 grams of a 62.3% (w/w) sucrose solution containing 0.23%by weight of sodium nitrite, set to be added over 30 minutes. Stage4—temperature was set at 35° C. and time was set for 10 minutesduration. Stage 5—temperature was set at 35° C., added to the nitricacid was 328.6 grams of a 62.3% (w/w) sucrose solution, set for aduration of 90 minutes. Stage 6—temperature was set at 35° C. andduration was set for 5 minutes. Stage 7—temperature was increased to 40°C. for a duration of 15 minutes. Stage 8—temperature was set at 40° C.and the time was set for a duration of 20 minutes. Stage 9—the reactionwas allowed to cool to 25° C. for a duration of 10 minutes. Once thereaction was programmed to proceed as indicated the reaction recipe wasinitiated and starting at stage 1, the reactor was closed to theatmosphere. When the reaction had progressed through all of the stages,the reaction mixture was removed from the reactor through the bottomvalve of the reactor.

Examples of, but not limited to, different work up procedures forremoval of nitric acid from a reaction mixture.

EXAMPLE 14 Nitric Acid Removal

In this work up procedure, the Mech-Chem Diffusion Dialysis AcidPurification System laboratory scale Model AP-L05 was used to separatethe nitric acid from organic product components in the reaction mixture(e.g., from Example 9). The Mech-Chem system contains two meteringpumps, the first being the acid reclaim pump and the second being theacid reject pump. The acid reject pump was set at 30% (pump length) and30% (pump speed) and the acid reclaim pump was set at 40% (pump length)and 40% (pump speed). This put the reclaim to acid reject ratio at about1.2. The system was first primed with RO (reverse osmosis) wateraccording to a standard setup procedure and then the water was removedfrom the acid tank in the unit. The acid tank was then filled with thediluted aqueous oxidation mixture and the water tank in the unit wasfilled with RO water. The acid purification unit was turned on with thepumps set as indicated and the process initiated. Over time, the dilutedreaction mixture was separated into two distinct streams, the acidrecovery stream and the product recovery stream.

EXAMPLE 15 Nitric Acid Removal

In this work up procedure, the reaction mixture (e.g., from Example 10)was concentrated at reduced pressure (rotary evaporator). The firstfraction distilled at ca. 23-34° C. and 50-120 millibar of pressure andcontained NOX gases as evidenced from the brown color of nitrogendioxide gas. The NOX gases were collected using a gas trap cooled withliquid nitrogen. The concentration of the reaction mixture continueduntil a viscous syrup remained. The liquid distillate was weighed (ca.390 g on average) and the same amount, ca. 390 g of deionized water wasadded to the viscous syrup mother liquor. Further separation of nitricacid from the organic product was carried out employing diffusiondialysis. The Mech-Chem Diffusion Dialysis Acid Purification Systemlaboratory scale model AP-105 was used to separate nitric acid form theorganic product. The same conditions as described above in Example 14were employed. Oxidation of liquid sugar solution as described above wasrepeated several times, each reaction mixture was mixed together with anaverage overall weight of 2.279 kg. Over a period of 24 hours ofprocessing, the entire oxidation mixture solution had been collected ineither the acid recovery stream or the product recovery stream.

Examples of, but not limited to, isolation procedures for salt productsfrom nitric acid oxidations of polyols illustrated in examples 9-13 andwork up procedures as illustrated in examples 14-15.

EXAMPLE 16 Isolation of Combined Oxidation Products as Sodium Salts fromNitric Acid Oxidation Example 11, and Work Up Procedure Example 15

The oxidation procedure described in Example 11 was carried out threetimes and the combined oxidation mixtures subjected to diffusiondialysis as illustrated in Example 15. Total amounts for the combinedoxidation reactions: Staley Dex 95-810.72 g, 4.500 mol (based upon 100%dextrose); HNO₃-846 mL, 13.5 mol. Upon completion of the diffusiondialysis, the organic acid solution was diluted to a total volume of 3.3L, the reclaimed nitric acid solution was concentrated to a total volumeof 190 mL. These were labeled as organic acid stock solution andreclaimed nitric acid stock solution. Organic acid stock solution (300mL) was chilled in an ice bath and titrated to a pH of 10 with aqueousNaOH (20 mL, 45% w/w). The solution, which became dark yellow, wasallowed to warm to room temperature. The pH of the solution dropped overtime but was maintained above 9 with additional NaOH (ca. 1 mL). Theresulting solution was refrigerated overnight resulting in a final pH of8.3. The solution was concentrated using a rotary evaporator and driedunder reduced pressure for 48 h to give a tan, amorphous solid. Thebasification procedure was carried out in triplicate. The average driedweight of solid product was 66.4 g±1.45 g. Using this average value, theweight of the crude solid sodium salts for the total organic acidsolution was calculated to be 730.4 g, 90.1% yield by weight.

EXAMPLE 17 Alcohol Precipitation of Combined Oxidation Products asSodium Salts from Nitric Acid Oxidation Example 11, and Work UpProcedure Example 15

A portion of dried crude solid sodium salt mixture (tan amorphous solid,ca. 5.0 g) from Example 16 was dissolved in water (5 mL) to form aviscous amber solution. solution. Methanol (50 mL) was added to thesolution and a tacky solid formed immediately. The mixture was stirredovernight without change in the appearance of the composition. Thesolution was decanted from the solid, and the solid was washed withmethanol (3×10 mL) and dried under reduced pressure. The filtrate andwashings were combined, concentrated using a rotary evaporator, anddried under reduced pressure. The precipitation procedure was carriedout in triplicate (17a-c, Table 5).

TABLE 5 Initial Solid Precipitate Dried Filtrate Recovered Solid SampleWeight (g) Weight (g) Weight (g) Weight (g) 17a 5.0063 4.6326 0.50885.1414 17b 5.0047 4.6438 0.5422 5.1860 17c 5.0018 4.6379 0.5500 5.1879

EXAMPLE 18 Isolation of Combined Oxidation Products as Sodium Salts fromNitric Acid Oxidation Example 12, and Work Up Procedure Example 15

The oxidation procedure described in Example 12 was carried out threetimes and the combined oxidation mixtures subjected to diffusiondialysis as illustrated in Example 15. Total amounts for the combinedoxidation reactions: Staley 1300-810.72 g, 4.500 mol (based upon 100%dextrose), HNO₃-846 mL, 13.5 mol. Upon completion of the diffusiondialysis, the organic acid solution was diluted to a total volume of2,640 mL. The streams from diffusion dialysis were labeled as organicacid stock solution and reclaimed nitric acid stock solution. Organicacid stock solution (300 mL, pH 1.2) was chilled in an ice bath andtitrated to a pH above 10 with aqueous NaOH (14 mL, 45% w/w). Thesolution, which became dark yellow, was allowed to warm to roomtemperature. The pH of the solution dropped over time but was maintainedabove 9 with additional NaOH (ca. 1 mL). The solution was cooledovernight resulting in a pH of 8. The solution pH was raised to above 9with NaOH, and the solution was concentrated using a rotary evaporatorand then dried under reduced pressure for 48 h to give a golden,amorphous solid. The basification procedure was carried out intriplicate. The average dried weight of solid product was 87.8 g±0.62 g.Using this average value, the weight of the crude solid sodium salts forthe total organic acid solution was calculated to be 772.6 g, 95.3%yield by weight.

EXAMPLE 19 Alcohol Precipitation of Combined Oxidation Products asSodium Salts from Nitric Acid Oxidation Example 12, and Work UpProcedure Example 15

A portion of dried solid crude sodium salt mixture (ca. 5.0 g) fromExample 18, was dissolved in water (5 mL) to form a viscous ambersolution. Methanol (50 mL) was added to the solution and a fine whiteprecipitate form immediately. The mixture was stirred overnight duringwhich time most of the syrup had solidified. The solid was isolated byfiltration, washed with methanol (3×10 mL), and dried under reducedpressure. The filtrate and washings were combined, concentrated using arotary evaporator, and dried under reduced pressure. The precipitationprocedure was carried out in triplicate (18a-c, Table 6).

TABLE 6 Initial Solid Precipitate Dried Filtrate Recovered Solid SampleWeight (g) Weight (g) Weight (g) Weight (g) 18a 5.0094 4.3130 0.84805.161 18b 5.0078 4.0448 0.8704 4.9152 18c 5.0073 4.3224 0.8650 5.1874

EXAMPLE 20 Isolation of Monopotassium D-Glucarate (MPG) from DiffusionDialysis Organic Acid Solution

Organic acid stock solution (Example 16, 900 mL, 963.2 g) wasconcentrated using a rotary evaporator. The resulting yellow solution(175 mL, 208.2 g) was diluted to 300 mL. A portion of the solution (100mL) was chilled in an ice bath and titrated from a pH of 1.8 to a pH of3.7 with aqueous KOH (45% by weight). The solution was refrigeratedovernight during which time a precipitate formed. The precipitate wasisolated by filtration, washed with cold water (3×10 mL), and driedunder reduced pressure to give MPG as a white powder. The precipitationprocedure was carried out in triplicate. The average dried weight ofsolid product was 6.61 g±0.41 g. Using this average value, the weight ofMPG for the total organic acid solution was calculated to be 72.7 g,0.293 mol, 9.0% yield by weight.

EXAMPLE 21 Isolation of Combined Oxidation Products Less MPG in Example20 as Potassium/Sodium Salts

The filtrate and washings from the isolation of monopotassiumD-glucarate (Example 20) were combined and chilled in an ice bath, thentitrated from a pH of 3.8 to a pH of 10 with aqueous NaOH (11 mL, 45%w/w). The solution, which became amber in color, was allowed to warm toroom temperature. The pH of the solution dropped over time but wasmaintained above 9 with additional NaOH (ca. 1 mL). The solution wasrefrigerated overnight resulting in a final pH of 9. The solution wasconcentrated using a rotary evaporator and dried under reduced pressurefor 48 h to give a light brown, amorphous solid. The basificationprocedure was carried out in triplicate. The average dried weight ofsolid product was 59.4 g±0.82 g. Using this average value, the weight ofthe crude solid potassium/sodium salts for the total organic acidsolution was calculated to be 653.4 g, 80.6% yield by weight.

EXAMPLE 22 Isolation of Monopotassium Glucarate (MPG) from DiffusionDialysis Reclaimed Acid

A portion of the reclaimed nitric acid stock solution (40 mL, Example16) was chilled in an ice bath and made basic with aqueous KOH (35 mL,45% by weight). The solution was allowed to warm to room temperature andthe pH was maintained above 9.5 with additional KOH. After stirring atroom temperature for 5 h, the solution was cooled overnight. Crystalsgrew from the solution during this time. The crystals were isolated byfiltration, washed with cold water (3×3 mL), and dried under reducedpressure to give potassium nitrate as colorless needles (5.80 g). Thefiltrate was chilled in an ice bath and back titrated to pH 3.7 withconcentrated HNO₃ (8 mL). Precipitate formed when the pH of the solutionfell below 5. The mixture was cooled overnight then the precipitate wasisolated by filtration, washed with cold water (3×5 mL), and dried underreduced pressure to give MPG as a white powder (19.13 g). The weight ofMPG for the total reclaimed nitric acid solution was calculated to be100.21 g, 0.3670 mol, 12.4% yield by weight.

EXAMPLE 23 Preparation of Sodium Potassium D-Glucarate fromMonopotassium D-Glucarate, Procedure 1 (Styron, 2002)

Aqueous sodium hydroxide solution (33 mL, 6 M) was added to a slurry ofmonopotassium D-glucarate (50.0 g, 0.201 mol) in water (150 mL) untilall of the solid dissolved and a constant pH of 9.7 was reached . Thesolution was concentrated to a syrup and seeded with the title compound.A solid crystalline cake formed over 24 h. The crystals were isolated byfiltration, washed with cold 1:1 ethanol/water (3×15 mL), and driedunder reduced pressure to give sodium potassium D-glucarate as colorlesscrystals (48.2 g, 0.157 mol as the dihydrate, 78.3%).

EXAMPLE 24 Preparation of Sodium Potassium D-Glucarate fromMonopotassium D-Glucarate, Procedure 2 (Styron, 2002)

Aqueous sodium hydroxide solution (21 mL, 2 M) was added to a slurry ofmonopotassium D-glucarate (1 0.0 g, 40.3 mmol) in water (50 mL) untilall of the solid dissolved and a constant pH of 10 was reached. Thevolume of the solution was reduced to 20 mL by rotary evaporator.Methanol (15 mL) was added, producing a cloudy solution which clearedupon heating. The solution was allowed to sit undisturbed at 5° C.Crystals grew from the solution over a 48 h period. The crystals wereisolated by filtration, washed with cold 1:1 methanol/water (3×5 mL),and dried under reduced pressure to give sodium potassium D-glucarate ascolorless crystals (10.2 g, 33.2 mmol as the dihydrate, 82.4%).

EXAMPLE 25 Preparation of Dipotassium D-Glucarate from MonopotassiumD-Glucarate (Styron, 2002)

Aqueous potassium hydroxide solution (27 mL, 2 M) was added to a slurryof monopotassium D-glucarate (10.2 g, 41.1 mmol) in water (50 mL) untilall of the solid dissolved and a constant pH of 10 was reached. Thesolution was concentrated to a syrup and seeded with the title compound.Crystals grew slowly from the syrup. After two weeks, the crystals wereisolated by filtration, washed with cold 1:1 ethanol/water (3×5 mL), anddried under reduced pressure to give dipotassium D-glucarate ascolorless crystals (8.14 g, 26.8 mmol as the monohydrate, 65.1%).

It is understood that the foregoing examples are merely illustrative ofthe present invention. Certain modifications of the articles and/ormethods employed may be made and still achieve the objectives of theinvention. Such modifications are contemplated as within the scope ofthe claimed invention.

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1. A corrosion inhibiting composition for metal comprising at least oneorganic acid salt prepared by a method comprising the steps of: a)preparing an aqueous solution of at least one organic compound suitablefor nitric acid oxidation; b) combining, over time, the aqueous solutionof the at least one organic compound and an aqueous solution of nitricacid to oxidize the at least one organic compound to at least oneorganic acid; c) removing a portion of the nitric acid from the combinedaqueous solution through an evaporation process; and d) making basicwith at least one base the solution from which nitric acid has beenremoved to convert residual nitric acid to inorganic nitrate and toconvert the at least one organic acid to the at least one organic acidsalt.
 2. The corrosion inhibiting composition of claim 1, wherein saidthe at least one organic compound suitable for nitric acid oxidation isselected from the group consisting of diols, triols, polyols, andcarbohydrates.
 3. The corrosion inhibiting composition of claim 1,wherein said method further comprises the steps of, after step c):removing additional nitric acid from the combined aqueous solution bydiffusion dialysis.
 4. The corrosion inhibiting composition of claim 1,wherein said at least one organic acid comprises glucaric acid, saidmethod further comprises the steps of, after step c): adding a potassiumbase to the solution from which nitric acid has been removed toneutralize residual nitric acid and to convert a portion of the glucaricacid to glucaric acid monopotassium salt; and removing at least some ofthe glucaric acid monopotassium salt from said at least one organicacid.
 5. The corrosion inhibiting composition of claim 4, wherein saidpotassium base is selected from the group consisting of: potassiumhydroxide, potassium hydride, potassium carbonate, potassiumbicarbonate, dipotassium phosphate, tripotassium phosphate, andpotassium acetate.
 6. The corrosion inhibiting composition of claim 3,wherein said at least one organic acid comprises glucaric acid, saidmethod further comprises the steps of, after diffusion dialysis: addinga potassium base to the solution from which nitric acid has been removedto neutralize residual nitric acid and to convert a portion of theglucaric acid to glucaric acid monopotassium salt; and removing at leastsome of the glucaric acid monopotassium salt from said at least oneorganic acid.
 7. The corrosion inhibiting composition of claim 6,wherein said potassium base is selected from the group consisting of:potassium hydroxide, potassium hydride, potassium carbonate, potassiumbicarbonate, dipotassium phosphate, tripotassium phosphate, andpotassium acetate.
 8. The corrosion inhibiting composition of claim 1,wherein said at least one organic acid salt is a neutralized acidselected from the group consisting of: aliphatic carboxylic acids,hydroxycarboxylic acids, aldonic acids, uronic acids, aldaric acids,keto-aldonic acids, keto-uronic acids, keto-aldaric acids, glucaricacid, mannaric acid, xylaric acid, arabinaric acid, and galactaric acid.9. The corrosion inhibiting composition of claim 1, wherein said atleast one organic acid salt is selected from the group consisting of:sodium potassium D-glucarate dihydrate and dipotassium D-glucaratehydrate.
 10. The corrosion inhibiting composition of claim 1, whereinsaid base is selected from the group consisting of: sodium hydroxide,potassium hydroxide, magnesium hydroxide, calcium hydroxide, lithiumhydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate,lithium carbonate, calcium carbonate, and magnesium carbonate.
 11. Adeicer composition comprising at least one deicing agent and at leastone organic acid salt prepared by a method comprising the steps of: a)preparing an aqueous solution of at least one organic compound suitablefor nitric acid oxidation; b) combining, over time, the aqueous solutionof the at least one organic compound and an aqueous solution of nitricacid to oxidize the at least one organic compound to at least oneorganic acid; c) removing a portion of the nitric acid from the combinedaqueous solution through an evaporation process; and d) making basicwith at least one base the solution from which nitric acid has beenremoved to convert residual nitric acid to inorganic nitrate and toconvert the at least one organic acid to the at least one organic acidsalt.
 12. The deicer composition of claim 11, wherein said the at leastone organic compound suitable for nitric acid oxidation is selected fromthe group consisting of diols, triols, polyols, and carbohydrates. 13.The deicer composition of claim 1, wherein said method of furthercomprises the steps of, after step c): removing additional nitric acidfrom the combined aqueous solution by diffusion dialysis.
 14. The deicercomposition of claim 11, wherein said at least one organic acidcomprises glucaric acid, said method further comprises the steps of,after step c): adding a potassium base to the solution from which nitricacid has been removed to neutralize residual nitric acid and to converta portion of the glucaric acid to glucaric acid monopotassium salt; andremoving at least some of the glucaric acid monopotassium salt from saidat least one organic acid.
 15. The deicer composition of claim 14,wherein said potassium base is selected from the group consisting of:potassium hydroxide, potassium hydride, potassium carbonate, potassiumbicarbonate, dipotassium phosphate, tripotassium phosphate, andpotassium acetate.
 16. The deicer composition of claim 13, wherein saidat least one organic acid comprises glucaric acid, said method furthercomprises the steps of, after diffusion dialysis: adding a potassiumbase to the solution from which nitric acid has been removed toneutralize residual nitric acid and to convert a portion of the glucaricacid to glucaric acid monopotassium salt; and removing at least some ofthe glucaric acid monopotassium salt from said at least one organicacid.
 17. The deicer composition of claim 16, wherein said potassiumbase is selected from the group consisting of: potassium hydroxide,potassium hydride, potassium carbonate, potassium bicarbonate,dipotassium phosphate, tripotassium phosphate, and potassium acetate.18. The deicer composition of claim 11, wherein said at least oneorganic acid salt is a neutralized acid selected from the groupconsisting of: aliphatic carboxylic acids, hydroxycarboxylic acids,aldonic acids, uronic acids, aldaric acids, keto-aldonic acids,keto-uronic acids, keto-aldaric acids, glucaric acid, mannaric acid,xylaric acid, arabinaric acid, and galactaric acid.
 19. The deicercomposition of claim 11, wherein said at least one organic acid salt isselected from the group consisting of: sodium potassium D-glucaratedihydrate and dipotassium D-glucarate hydrate.
 20. The deicercomposition of claim 11, wherein said at least one base is selected fromthe group consisting of: sodium hydroxide, potassium hydroxide,magnesium hydroxide, calcium hydroxide, lithium hydroxide, ammoniumhydroxide, sodium carbonate, potassium carbonate, lithium carbonate,calcium carbonate, and magnesium carbonate.
 21. The deicer compositionof claim 11, wherein said at least one deicing agent is selected fromthe group consisting of: sodium chloride, magnesium chloride, sodiumacetate, potassium acetate, calcium magnesium acetate, and calciumchloride.
 22. A concrete admixture composition comprising at least oneorganic acid salt prepared by a method comprising the steps of: a)preparing an aqueous solution of at least one organic compound suitablefor nitric acid oxidation; b) combining, over time, the aqueous solutionof the at least one organic compound and an aqueous solution of nitricacid to oxidize the at least one organic compound to at least oneorganic acid; c) removing a portion of the nitric acid from the combinedaqueous solution through an evaporation process; and d) making basicwith at least one base the solution from which nitric acid has beenremoved to convert residual nitric acid to inorganic nitrate and toconvert the at least one organic acid to the at least one organic acidsalt.
 23. The concrete admixture composition of claim 22, wherein saidthe at least one organic compound suitable for nitric acid oxidation isselected from the group consisting of diols, triols, polyols, andcarbohydrates.
 24. The concrete admixture composition of claim 22,wherein said method further comprises the steps of, after step c):removing additional nitric acid from the combined aqueous solution bydiffusion dialysis.
 25. The concrete admixture composition of claim 22,wherein said at least one organic acid comprises glucaric acid, saidmethod further comprises the steps of, after step c): adding a potassiumbase to the solution from which nitric acid has been removed toneutralize residual nitric acid and to convert a portion of the glucaricacid to glucaric acid monopotassium salt; and removing at least some ofthe glucaric acid monopotassium salt from said at least one organicacid.
 26. The concrete admixture composition of claim 25, wherein saidpotassium base is selected from the group consisting of: potassiumhydroxide, potassium hydride, potassium carbonate, potassiumbicarbonate, dipotassium phosphate, tripotassium phosphate, andpotassium acetate.
 27. The concrete admixture of claim 24, wherein saidat least one organic acid comprises glucaric acid, said method furthercomprises the steps of, after diffusion dialysis: adding a potassiumbase to the solution from which nitric acid has been removed toneutralize residual nitric acid and to convert a portion of the glucaricacid to glucaric acid monopotassium salt; and removing at least some ofthe glucaric acid monopotassium salt from said at least one organicacid.
 28. The concrete admixture composition of claim 27, wherein saidpotassium base is selected from the group consisting of: potassiumhydroxide, potassium hydride, potassium carbonate, potassiumbicarbonate, dipotassium phosphate, tripotassium phosphate, andpotassium acetate.
 29. The concrete admixture composition of claim 22,wherein said at least one organic acid salt is a neutralized acidselected from the group consisting of: aliphatic carboxylic acids,hydroxycarboxylic acids, aldonic acids, uronic acids, aldaric acids,keto-aldonic acids, keto-uronic acids, keto-aldaric acids, glucaricacid, mannaric acid, xylaric acid, arabinaric acid, and galactaric acid.30. The concrete admixture composition of claim 22 wherein said at leastone organic acid salt is selected from the group consisting of: sodiumpotassium D-glucarate dihydrate and dipotassium D-glucarate hydrate. 31.The concrete admixture composition of claim 22, wherein said base isselected from the group consisting of: sodium hydroxide, potassiumhydroxide, magnesium hydroxide, calcium hydroxide, lithium hydroxide,ammonium hydroxide, sodium carbonate, potassium carbonate, lithiumcarbonate, calcium carbonate, and magnesium carbonate.
 32. The concreteadmixture composition of claim 22, wherein said admixture serves as aconcrete set retarder.
 33. The concrete admixture composition of claim22, wherein said admixture serves as a concrete water reducer.
 34. Theconcrete admixture composition of claim 22, wherein said admixtureserves as a concrete set retarder and water reducer.
 35. A method forpreparing an aqueous solution of at least one organic compound suitablefor direct nitric acid oxidation comprising the steps of: adding atleast one polysaccharide to aqueous nitric acid; stirring the resultingmixture until the polysaccharide is hydrolyzed to lower molecular weightsaccharides selected from the group consisting of: smaller than the atleast one polysaccharide, oligosaccharides, tetrasaccharides,trisaccharides, disaccharides, and monosaccharides.